1. Field of the Invention
The present invention relates to a solar cell of high efficiency, a method of producing the same and an apparatus for producing a semiconductor.
2. Disscussion of Background
It has been essential to obtain a silicon solar cell of high efficiency by forming minute projections and recesses in a substrate surface so that incident light entering from the substrate surface can efficiently be taken in the inside of the solar cell. Various methods have been proposed to realize such solar cell.
In a solar cell of single crystal silicon, minute pyramidal projections and recesses called a texture structure are formed by a wet etching method by using an aqueous alkali solution such as caustic soda, caustic potash or the like. With the texture structure constituted by many inclined planes, light reflected at a surface hits a surface of another position and re-enters into the inside whereby the light is absorbed efficiently in the solar cell. A part of the incident light reaches the rear surface without being absorbed in the substrate. Such light is reflected at the rear surface to reach again the front surface where the texture structure is formed. Accordingly, the light is reflected again at an inclined plane and confined in the solar cell. Thus, a substantial part of light is absorbed in the solar cell to thereby improve the characteristics of the solar cell. However, this technic utilizes a difference of etching rate at crystal planes in a silicon crystal. Namely, the etching rate obtained by using an aqueous alkali solution is the fastest at a (100) plane of silicon and the slowest at a (111) plane. Accordingly, when etching is effected to a (100) plane as the initial plane and if a (111) plane is produced due to any incident during the etching process, the (111) plane which delays the etching rate remains dominantly in the surface as a dominant plane. Since the (111) plane has an inclination of about 54 degree to the (100) plane, pyramidal projections each constituted by only (111), (111) and (111) planes which are equivalent to the (111) plane are formed at the final stage of the process. The process will be described in more detail. A substrate of silicon having a (100) plane at its surface is dipped in an aqueous solution of caustic potash or caustic soda having a concentration of from several % to 10 and several % heated to 60xc2x0 C. to 95xc2x0 C. for 10 min to 30 min. In some cases, isopropyl alcohol of 5% to 30% by volume per an aqueous alkali solution may be added. After the dipping, the substrate is taken out and is washed with water.
In a case of using a substrate of polycrystal silicon which has a variety of directions of crystal in a plane, a pyramidal structure is formed in perpendicular to the (100) plane. Accordingly, planes appearing in the front surface are in random directions, and a sufficient light confining effect as obtained in the substrate of single crystal can not be expected. Further, when the etching liquid having the above-mentioned composition is used, the depth of etching varies depending on the plane directions exposed at the front surface, and there produce steps which do not provide an antireflection effect and prohibits formation of effective electrodes. Accordingly, various technics of forming the texture structure have been studied for the substrate of polycrystal silicon, other than the etching method using an aqueous alkali solution for the silicon substrate of single crystal. Further, the conventional method requires a long time for the treatment and is not high in productivity. For example, the conventional method requires a treating time of about 30 min in order to form stably a texture structure in the substrate of single crystal silicon dipped in an etching liquid prepared by adding isopropyl alcohol of 30% by volume to a 1% aqueous potassium hydroxide solution, which is heated to 90xc2x0 C.
As a first example, there is proposed a method disclosed in Japanese publication JP-B-7-105518 wherein a projection/recess structure is formed by forming mechanically V-like grooves in the front surface of a solar cell of polycrystal silicon. FIG. 13 shows in cross section the structure formed in this example.
As a second example, there is proposed a method disclosed in 9th International Photovoltaic Science and Engineering held on Nov., 11 to 15, 1996 wherein a pyramidal structure is formed in the front surface of a solar cell of polycrystal silicon by an etching method called RIE (Reactive Ion Etching). FIG. 14 shows a microphotograph of a projection/recess structure formed by RIE.
The detail of the above-mentioned examples will be described.
In the method of mechanically forming the V-like grooves in the first example, a plurality of rotating blades in which material having a hardness higher than silicon, such as diamond, silicon carbide or the like is embedded, are pushed to the silicon substrate, and the rotating blades are drugged on the substrate to thereby form the V-like grooves in the surface of the substrate. The pitch of the V-like grooves is generally in a range of from several hundred xcexcm to several mm, which is adjustable by adjusting the distance of the blades. The depth of the V-like grooves is generally from several ten xcexcm to 100 xcexcm. After the mechanically forming the grooves, the substrate is dipped in a solution such as an aqueous alkali solution or the like which is capable of etching silicon whereby a defective crystal layer produced in an area to which the blades have been in mechanical contact, is removed.
In the method of forming projections and recesses by RIE as in the second example, a chlorine gas is used as an etching gas, and silicon is reacted with chlorine ions and chlorine radicals produced by plasma under a reduced pressure to form a chloride of silicon so that the silicon is removed by evaporation. Although a mechanism of forming the projection/recess structure is unclear because the publication fails to disclose it, it is supposed that a part of the silicon chloride as a reaction product remains in the front surface because the etching is conducted without using an etching mask, and cylindrical projections are formed by utilizing the reaction product as a micro-mask. After the formation of the projection/recess structure in the front surface, the substrate is subjected to a wet type cleaning so that the reaction product and so on remaining on the front surface is removed. Thus, a series of treatments is finished.
The conventional method of forming mechanically the V-like grooves required the grinding treatment for each wafer, and there was a problem in large scale production. Further, the conventional technic required a step of removing the defective layer by the wet type etching because there was a defect in the surface portion of crystal when the V-like grooves were formed. In order to obtain effectively a light confining effect, it is necessary to form deep V-like grooves. However, the grooves can not be formed with a small distance because the pitch of the V-like grooves is restricted by the pich of the rotating blades. On the other hand, the substrate has to be thin in order to reduce the cost of material. Accordingly, a crack may be produced in the substrate, or breakage may be caused during manufacturing steps when deep grooves are formed in the substrate.
In the method by using RIE, the problem of producing a defective crystal as in the case of forming the V-like grooves can be avoided. However, there are problems such as a high manufacturing cost due to use of a vacuum device and a poor productivity due to a small performance of treatment.
It is an object of the present invention to provide a silicon solar cell having a high light confining effect wherein a minute projection/recess structure is formed in a silicon substrate plane of single crystal or polycrystal by a wet type etching.
It is an object of the present invention to provide a method of producing a silicon solar cell with high productivity.
Further, it is an object of the present invention to provide an apparatus for producing a silicon solar cell.
In accordance with a first aspect of the present invention, there is provided a method of producing a solar cell characterized by preparing an aqueous solution of mixed acid of hydrofluoric acid, nitric acid and an adjusting agent containing at least phosphoric acid or a water-soluble carboxylic acid having a small member of carbon atoms which is capable of adjusting an etching rate, and dipping a silicon substrate in the aqueous solution of mixed acid as an etching liquid whereby minute projections and recesses are formed in a surface of the silicon substrate.
In the method of producing a solar cell according to a second aspect of the present invention, the adjusting agent is in a predetermined amount for effecting etching at a high rate in a stable manner without changing a shape obtained by etching.
In the method of producing a solar cell according to a third aspect of the present invention, ammonium fluoride is added to the aqueous solution of mixed acid to form an etching liquid.
In the method of the producing a solar cell according to a fourth aspect of the present invention, the carboxylic acid is composed of at least one selected from the group consisting of propionic acid, butyric acid, valoric acid, caproic acid, tartaric acid, succinic acid, adipic acid, propane-tricarboxylic acid and an isomer of propane-tricarboxylic acid.
In the method of producing a solar cell according to a fifth aspect, a surface active agent is added to the aqueous solution of mixed acid to prepare an etching liquid.
In the method of producing a solar cell according to a sixth aspect, the surface active agent is composed of at least one selected from the group consisting of a nonionic surface active agent, an anionic surface active agent and a cationic surface active agent.
In the method of producing a solar cell according to a seventh aspect, the silicon substrate is dipped in an aqueous caustic alkali solution after the etching treatment has been conducted with the aqueous solution of mixed acid.
In the method of producing a solar cell according to an eighth aspect, the aqueous caustic alkali solution is an aqueous solution of caustic potash or caustic soda having a concentration of 1 to 50%, which is used under a temperature condition in a range of from the room temperature to 95xc2x0 C.
In accordance with a ninth aspect of the present invention, there is provided a method of producing a solar cell characterized by preparing an aqueous solution of mixed acid of hydrofluoric acid, nitric acid and an adjusting agent. containing phosphoric acid or a water-soluble carboxylic acid having a carbon atom number of 3 to 6 which is capable of adjusting an etching rate; dipping a silicon substrate in the aqueous solution of mixed acid as an etching liquid; and dipping the silicon substrate in a mixed water solution of caustic alkali and isopropyl alcohol.
In the method of producing a solar cell according to a tenth aspect of the invention, a plurality of silicon substrates undergo an etching treatment in a state that the rear surfaces of the substrates are contacted with each other.
In accordance with an eleventh aspect of the present invention, there is provided a solar cell comprising a substrate of single crystal or polycrystal, the solar cell being characterized in that a spherical recess wherein the ratio of the depth to the diameter is in a range of from 0.2 to 0.45 is continuously formed in a surface of the substrate.
In the solar cell according to a twelfth aspect of the invention, the spherical recess as in the eleventh aspect is continuously formed in at least a surface to which light is incident.
In accordance with a thirteenth aspect of the present invention, there is provided a solar cell comprising a substrate of single crystal or polycrystal, the solar cell being characterized in that spherical recesses wherein the ratio of the depth to the diameter is in a range of from 0.2 to 0.45, and minute pyramidal projections and recesses are formed in a surface of the substrate.
In accordance with a fourteenth aspect of the present invention, there is provided an apparatus for producing a semiconductor which is composed of an etching device in which a silicon substrate is dipped in an etching liquid composed of an aqueous solution of mixed acid of hydrofluoric acid, nitric acid and an adjusting agent containing phosphoric acid or a water-soluble carboxylic acid having a carbon atom number of 3 to 6, and a detecting means for detecting a concentration of the nitric acid in the aqueous solution of mixed acid.
In the apparatus for a producing a semiconductor according to a fifteenth aspect of the invention, a nitric acid supply means is provided to control an amount of the nitric acid to maintain a concentration of the nitric acid to be in a predetermined range.
In accordance with a sixteenth aspect of the present invention, there is provided an apparatus for producing a semiconductor which is composed of an etching device in which a silicon substrate is dipped in an etching liquid composed of an aqueous solution of mixed acid of hydrofluoric acid, nitric acid and an adjusting agent containing at least phosphoric acid or a water-soluble carboxylic acid having a carbon atom number of 3 to 6 which is capable of adjusting an etching rate, and a substrate holder for holding the silicon substrate in an upright direction when the silicon substrate is etched in the etching device.
In accordance with a seventeenth aspect of the present invention, there is provided an apparatus for producing a semiconductor which is composed of an etching device in which a silicon substrate is dipped in an etching liquid composed of an aqueous solution of mixed acid of hydrofluoric acid, nitric acid and an adjusting agent containing at least phosphoric acid or a water-soluble carboxylic acid having a carbon atom number of 3 to 6 which is capable of adjusting an etching rate, and a substrate holder for holding a plurality of silicon substrates in an upright direction with the rear surfaces of the silicon substrates in mutual contact when the silicon substrate is etched in the etching device.